Homomeric chains of intermolecular bonds scaffold octahedral germanium perovskites.

Perovskites with low ionic radii metal centres (for example, Ge perovskites) experience both geometrical constraints and a gain in electronic energy through distortion; for these reasons, synthetic attempts do not lead to octahedral [GeI6] perovskites, but rather, these crystallize into polar non-perovskite structures1-6. Here, inspired by the principles of supramolecular synthons7,8, we report the assembly of an organic scaffold within perovskite structures with the goal of influencing the geometric arrangement and electronic configuration of the crystal, resulting in the suppression of the lone pair expression of Ge and templating the symmetric octahedra. We find that, to produce extended homomeric non-covalent bonding, the organic motif needs to possess self-complementary properties implemented using distinct donor and acceptor sites. Compared with the non-perovskite structure, the resulting [GeI6]4- octahedra exhibit a direct bandgap with significant redshift (more than 0.5 eV, measured experimentally), 10 times lower octahedral distortion (inferred from measured single-crystal X-ray diffraction data) and 10 times higher electron and hole mobility (estimated by density functional theory). We show that the principle of this design is not limited to two-dimensional Ge perovskites; we implement it in the case of copper perovskite (also a low-radius metal centre), and we extend it to quasi-two-dimensional systems. We report photodiodes with Ge perovskites that outperform their non-octahedral and lead analogues. The construction of secondary sublattices that interlock with an inorganic framework within a crystal offers a new synthetic tool for templating hybrid lattices with controlled distortion and orbital arrangement, overcoming limitations in conventional perovskites.

Molecular surface programming of rectifying junctions between InAs colloidal quantum dot solids.

Heavy-metal-free III-V colloidal quantum dots (CQDs) show promise in optoelectronics: Recent advancements in the synthesis of large-diameter indium arsenide (InAs) CQDs provide access to short-wave infrared (IR) wavelengths for three-dimensional ranging and imaging. In early studies, however, we were unable to achieve a rectifying photodiode using CQDs and molybdenum oxide/polymer hole transport layers, as the shallow valence bandedge (5.0 eV) was misaligned with the ionization potentials of the widely used transport layers. This occurred when increasing CQD diameter to decrease the bandgap below 1.1 eV. Here, we develop a rectifying junction among InAs CQD layers, where we use molecular surface modifiers to tune the energy levels of InAs CQDs electrostatically. Previously developed bifunctional dithiol ligands, established for II-VI and IV-VI CQDs, exhibit slow reaction kinetics with III-V surfaces, causing the exchange to fail. We study carboxylate and thiolate binding groups, united with electron-donating free end groups, that shift upward the valence bandedge of InAs CQDs, producing valence band energies as shallow as 4.8 eV. Photophysical studies combined with density functional theory show that carboxylate-based passivants participate in strong bidentate bridging with both In and As on the CQD surface. The tuned CQD layer incorporated into a photodiode structure achieves improved performance with EQE (external quantum efficiency) of 35% (>1 µm) and dark current density < 400 nA cm-2, a >25% increase in EQE and >90% reduced dark current density compared to the reference device. This work represents an advance over previous III-V CQD short-wavelength IR photodetectors (EQE < 5%, dark current > 10,000 nA cm-2).

Lattice anchoring stabilizes solution-processed semiconductors.

The stability of solution-processed semiconductors remains an important area for improvement on their path to wider deployment. Inorganic caesium lead halide perovskites have a bandgap well suited to tandem solar cells1 but suffer from an undesired phase transition near room temperature2. Colloidal quantum dots (CQDs) are structurally robust materials prized for their size-tunable bandgap3; however, they also require further advances in stability because they are prone to aggregation and surface oxidization at high temperatures as a consequence of incomplete surface passivation4,5. Here we report 'lattice-anchored' hybrid materials that combine caesium lead halide perovskites with lead chalcogenide CQDs, in which lattice matching between the two materials contributes to a stability exceeding that of the constituents. We find that CQDs keep the perovskite in its desired cubic phase, suppressing the transition to the undesired lattice-mismatched phases. The stability of the CQD-anchored perovskite in air is enhanced by an order of magnitude compared with pristine perovskite, and the material remains stable for more than six months at ambient conditions (25 degrees Celsius and about 30 per cent humidity) and more than five hours at 200 degrees Celsius. The perovskite prevents oxidation of the CQD surfaces and reduces the agglomeration of the nanoparticles at 100 degrees Celsius by a factor of five compared with CQD controls. The matrix-protected CQDs show a photoluminescence quantum efficiency of 30 per cent for a CQD solid emitting at infrared wavelengths. The lattice-anchored CQD:perovskite solid exhibits a doubling in charge carrier mobility as a result of a reduced energy barrier for carrier hopping compared with the pure CQD solid. These benefits have potential uses in solution-processed optoelectronic devices.

Ligand Exchange at a Covalent Surface Enables Balanced Stoichiometry in III-V Colloidal Quantum Dots.

III-V colloidal quantum dots (CQDs) are promising semiconducting materials for optoelectronic applications; however, their strong covalent character requires a distinct approach to surface management compared with widely investigated II-VI and IV-VI CQDs-dots, which by contrast are characterized by an ionic nature. Here we show stoichiometric reconstruction in InAs CQDs by ligand exchange. In particular, we find that indium-carboxylate ligands, which passivate as-synthesized InAs CQDs and are responsible for In-rich surfaces, can be replaced by anionic ligands such as thiols. This enables the production of inks consisting of balanced-stoichiomety CQDs; this is distinct from what is observed in II-VI and IV-VI CQDs, in which thiols replace carboxylates. The approach enables the implementation of InAs CQD solids as the active layer in photodiode detectors that exhibit an external quantum efficiency of 36% at 930 nm and a photoresponse time of 65 ns, which is 4 times shorter than that of reference PbS CQD devices.

Bright and Stable Light-Emitting Diodes Based on Perovskite Quantum Dots in Perovskite Matrix.

Light-emitting diodes (LEDs) based on metal halide perovskite quantum dots (QDs) have achieved impressive external quantum efficiencies; however, the lack of surface protection of QDs, combined with efficiency droop, decreases device operating lifetime at brightnesses of interest. The epitaxial incorporation of QDs within a semiconducting shell provides surface passivation and exciton confinement. Achieving this goal in the case of perovskite QDs remains an unsolved challenge in view of the materials' chemical instability. Here, we report perovskite QDs that remain stable in a thin layer of precursor solution of perovskite, and we use strained QDs as nucleation centers to drive the homogeneous crystallization of a perovskite matrix. Type-I band alignment ensures that the QDs are charge acceptors and radiative emitters. The new materials show suppressed Auger bi-excition recombination and bright luminescence at high excitation (600 W cm-2), whereas control materials exhibit severe bleaching. Primary red LEDs based on the new materials show an external quantum efficiency of 18%, and these retain high performance to brightnesses exceeding 4700 cd m-2. The new materials enable LEDs having an operating half-life of 2400 h at an initial luminance of 100 cd m-2, representing a 100-fold enhancement relative to the best primary red perovskite LEDs.

Ternary Alloys Enable Efficient Production of Methoxylated Chemicals via Selective Electrocatalytic Hydrogenation of Lignin Monomers.

We explore the selective electrocatalytic hydrogenation of lignin monomers to methoxylated chemicals, of particular interest, when powered by renewable electricity. Prior studies, while advancing the field rapidly, have so far lacked the needed selectivity: when hydrogenating lignin-derived methoxylated monomers to methoxylated cyclohexanes, the desired methoxy group (-OCH3) has also been reduced. The ternary PtRhAu electrocatalysts developed herein selectively hydrogenate lignin monomers to methoxylated cyclohexanes-molecules with uses in pharmaceutics. Using X-ray absorption spectroscopy and in situ Raman spectroscopy, we find that Rh and Au modulate the electronic structure of Pt and that this modulating steers intermediate energetics on the electrocatalyst surface to facilitate the hydrogenation of lignin monomers and suppress C-OCH3 bond cleavage. As a result, PtRhAu electrocatalysts achieve a record 58% faradaic efficiency (FE) toward 2-methoxycyclohexanol from the lignin monomer guaiacol at 200 mA cm-2, representing a 1.9× advance in FE and a 4× increase in partial current density compared to the highest productivity prior reports. We demonstrate an integrated lignin biorefinery where wood-derived lignin monomers are selectively hydrogenated and funneled to methoxylated 2-methoxy-4-propylcyclohexanol using PtRhAu electrocatalysts. This work offers an opportunity for the sustainable electrocatalytic synthesis of methoxylated pharmaceuticals from renewable biomass.

Ligand-Assisted Reconstruction of Colloidal Quantum Dots Decreases Trap State Density.

Increasing the power conversion efficiency (PCE) of colloidal quantum dot (CQD) solar cells has relied on improving the passivation of CQD surfaces, enhancing CQD coupling and charge transport, and advancing device architecture. The presence of hydroxyl groups on the nanoparticle surface, as well as dimers-fusion between CQDs-has been found to be the major source of trap states, detrimental to optoelectronic properties and device performance. Here, we introduce a CQD reconstruction step that decreases surface hydroxyl groups and dimers simultaneously. We explored the dynamic interaction of charge carriers between band-edge states and trap states in CQDs using time-resolved spectroscopy, showing that trap to ground-state recombination occurs mainly from surface defects in coupled CQD solids passivated using simple metal halides. Using CQD reconstruction, we demonstrate a 60% reduction in trap density and a 25% improvement in charge diffusion length. These translate into a PCE of 12.5% compared to 10.9% for control CQDs.

Acid-Assisted Ligand Exchange Enhances Coupling in Colloidal Quantum Dot Solids.

Colloidal quantum dots (CQDs) are promising solution-processed infrared-absorbing materials for optoelectronics. In these applications, it is crucial to replace the electrically insulating ligands used in synthesis to form strongly coupled quantum dot solids. Recently, solution-phase ligand-exchange strategies have been reported that minimize the density of defects and the polydispersity of CQDs; however, we find herein that the new ligands exhibit insufficient chemical reactivity to remove original oleic acid ligands completely. This leads to low CQD packing and correspondingly low electronic performance. Here we report an acid-assisted solution-phase ligand-exchange strategy that, by enabling efficient removal of the original ligands, enables the synthesis of densified CQD arrays. Our use of hydroiodic acid simultaneously facilitates high CQD packing via proton donation and CQD passivation through iodine. We demonstrate highly packed CQD films with a 2.5 times increased carrier mobility compared with prior exchanges. The resulting devices achieve the highest infrared photon-to-electron conversion efficiencies (>50%) reported in the spectral range of 0.8 to 1.1 eV.

Metal-Organic Frameworks Mediate Cu Coordination for Selective CO2 Electroreduction.

The electrochemical carbon dioxide reduction reaction (CO2RR) produces diverse chemical species. Cu clusters with a judiciously controlled surface coordination number (CN) provide active sites that simultaneously optimize selectivity, activity, and efficiency for CO2RR. Here we report a strategy involving metal-organic framework (MOF)-regulated Cu cluster formation that shifts CO2 electroreduction toward multiple-carbon product generation. Specifically, we promoted undercoordinated sites during the formation of Cu clusters by controlling the structure of the Cu dimer, the precursor for Cu clusters. We distorted the symmetric paddle-wheel Cu dimer secondary building block of HKUST-1 to an asymmetric motif by separating adjacent benzene tricarboxylate moieties using thermal treatment. By varying materials processing conditions, we modulated the asymmetric local atomic structure, oxidation state and bonding strain of Cu dimers. Using electron paramagnetic resonance (EPR) and in situ X-ray absorption spectroscopy (XAS) experiments, we observed the formation of Cu clusters with low CN from distorted Cu dimers in HKUST-1 during CO2 electroreduction. These exhibited 45% C2H4 faradaic efficiency (FE), a record for MOF-derived Cu cluster catalysts. A structure-activity relationship was established wherein the tuning of the Cu-Cu CN in Cu clusters determines the CO2RR selectivity.

Hybrid organic-inorganic inks flatten the energy landscape in colloidal quantum dot solids.

Bandtail states in disordered semiconductor materials result in losses in open-circuit voltage (Voc) and inhibit carrier transport in photovoltaics. For colloidal quantum dot (CQD) films that promise low-cost, large-area, air-stable photovoltaics, bandtails are determined by CQD synthetic polydispersity and inhomogeneous aggregation during the ligand-exchange process. Here we introduce a new method for the synthesis of solution-phase ligand-exchanged CQD inks that enable a flat energy landscape and an advantageously high packing density. In the solid state, these materials exhibit a sharper bandtail and reduced energy funnelling compared with the previous best CQD thin films for photovoltaics. Consequently, we demonstrate solar cells with higher Voc and more efficient charge injection into the electron acceptor, allowing the use of a closer-to-optimum bandgap to absorb more light. These enable the fabrication of CQD solar cells made via a solution-phase ligand exchange, with a certified power conversion efficiency of 11.28%. The devices are stable when stored in air, unencapsulated, for over 1,000 h.

Tailoring the Energy Landscape in Quasi-2D Halide Perovskites Enables Efficient Green-Light Emission.

Organo-metal halide perovskites are a promising platform for optoelectronic applications in view of their excellent charge-transport and bandgap tunability. However, their low photoluminescence quantum efficiencies, especially in low-excitation regimes, limit their efficiency for light emission. Consequently, perovskite light-emitting devices are operated under high injection, a regime under which the materials have so far been unstable. Here we show that, by concentrating photoexcited states into a small subpopulation of radiative domains, one can achieve a high quantum yield, even at low excitation intensities. We tailor the composition of quasi-2D perovskites to direct the energy transfer into the lowest-bandgap minority phase and to do so faster than it is lost to nonradiative centers. The new material exhibits 60% photoluminescence quantum yield at excitation intensities as low as 1.8 mW/cm2, yielding a ratio of quantum yield to excitation intensity of 0.3 cm2/mW; this represents a decrease of 2 orders of magnitude in the excitation power required to reach high efficiency compared with the best prior reports. Using this strategy, we report light-emitting diodes with external quantum efficiencies of 7.4% and a high luminescence of 8400 cd/m2.

Nanoimprint-Transfer-Patterned Solids Enhance Light Absorption in Colloidal Quantum Dot Solar Cells.

Colloidal quantum dot (CQD) materials are of interest in thin-film solar cells due to their size-tunable bandgap and low-cost solution-processing. However, CQD solar cells suffer from inefficient charge extraction over the film thicknesses required for complete absorption of solar light. Here we show a new strategy to enhance light absorption in CQD solar cells by nanostructuring the CQD film itself at the back interface. We use two-dimensional finite-difference time-domain (FDTD) simulations to study quantitatively the light absorption enhancement in nanostructured back interfaces in CQD solar cells. We implement this experimentally by demonstrating a nanoimprint-transfer-patterning (NTP) process for the fabrication of nanostructured CQD solids with highly ordered patterns. We show that this approach enables a boost in the power conversion efficiency in CQD solar cells primarily due to an increase in short-circuit current density as a result of enhanced absorption through light-trapping.

10.6% Certified Colloidal Quantum Dot Solar Cells via Solvent-Polarity-Engineered Halide Passivation.

Colloidal quantum dot (CQD) solar cells are solution-processed photovoltaics with broad spectral absorption tunability. Major advances in their efficiency have been made via improved CQD surface passivation and device architectures with enhanced charge carrier collection. Herein, we demonstrate a new strategy to improve further the passivation of CQDs starting from the solution phase. A cosolvent system is employed to tune the solvent polarity in order to achieve the solvation of methylammonium iodide (MAI) and the dispersion of hydrophobic PbS CQDs simultaneously in a homogeneous phase, otherwise not achieved in a single solvent. This process enables MAI to access the CQDs to confer improved passivation. This, in turn, allows for efficient charge extraction from a thicker photoactive layer device, leading to a certified solar cell power conversion efficiency of 10.6%, a new certified record in CQD photovoltaics.

Colloidal Quantum Dot Photovoltaics Enhanced by Perovskite Shelling.

Solution-processed quantum dots are a promising material for large-scale, low-cost solar cell applications. New device architectures and improved passivation have been instrumental in increasing the performance of quantum dot photovoltaic devices. Here we report photovoltaic devices based on inks of quantum dot on which we grow thin perovskite shells in solid-state films. Passivation using the perovskite was achieved using a facile solution ligand exchange followed by postannealing. The resulting hybrid nanostructure created a more intrinsic CQD film, which, when incorporated into a photovoltaic device with graded bandstructure, achieved a record solar cell performance for single-step-deposited CQD films, exhibiting an AM1.5 solar power conversion efficiency of 8.95%.

High-Efficiency Colloidal Quantum Dot Photovoltaics via Robust Self-Assembled Monolayers.

The optoelectronic tunability offered by colloidal quantum dots (CQDs) is attractive for photovoltaic applications but demands proper band alignment at electrodes for efficient charge extraction at minimal cost to voltage. With this goal in mind, self-assembled monolayers (SAMs) can be used to modify interface energy levels locally. However, to be effective SAMs must be made robust to treatment using the various solvents and ligands required for to fabricate high quality CQD solids. We report robust self-assembled monolayers (R-SAMs) that enable us to increase the efficiency of CQD photovoltaics. Only by developing a process for secure anchoring of aromatic SAMs, aided by deposition of the SAMs in a water-free deposition environment, were we able to provide an interface modification that was robust against the ensuing chemical treatments needed in the fabrication of CQD solids. The energy alignment at the rectifying interface was tailored by tuning the R-SAM for optimal alignment relative to the CQD quantum-confined electron energy levels. This resulted in a CQD PV record power conversion efficiency (PCE) of 10.7% with enhanced reproducibility relative to controls.

Pure Cubic-Phase Hybrid Iodobismuthates AgBi2 I7 for Thin-Film Photovoltaics.

Bismuth-based hybrid perovskites are candidates for lead-free and air-stable photovoltaics, but poor surface morphologies and a high band-gap energy have previously limited these hybrid perovskites. A new materials processing strategy to produce enhanced bismuth-based thin-film photovoltaic absorbers by incorporation of monovalent silver cations into iodobismuthates is presented. Solution-processed AgBi2 I7 thin films are prepared by spin-coating silver and bismuth precursors dissolved in n-butylamine and annealing under an N2 atmosphere. X-ray diffraction analysis reveals the pure cubic structure (Fd3m) with lattice parameters of a=b=c=12.223 Å. The resultant AgBi2 I7 thin films exhibit dense and pinhole-free surface morphologies with grains ranging in size from 200-800 nm and a low band gap of 1.87 eV suitable for photovoltaic applications. Initial studies produce solar power conversion efficiencies of 1.22 % and excellent stability over at least 10 days under ambient conditions.

Tailoring the Electronic Properties of Colloidal Quantum Dots in Metal-Semiconductor Nanocomposites for High Performance Photodetectors.

Metallic nanoparticles tailor the electronic properties of PbS colloidal quantum dots in a post-synthetic, all solution-processable approach. The Fermi level of the resulting nanocomposites can be tuned from p- to n-type due to remote charge transfer and electron trap state passivation. This concurrently reduces dark current, improves time response, and increases sensitivity in PbS photoconductors, yielding an over-two-fold increase in detectivity.

Metal-insulator-semiconductor heterostructures for plasmonic hot-carrier optoelectronics.

Plasmonic hot-electron devices are attractive candidates for light-energy harvesting and photodetection applications. For solid state devices, the most compact and straightforward architecture is the metal-semiconductor Schottky junction. However convenient, this structure introduces limitations such as the elevated dark current associated to thermionic emission, or constraints for device design due to the finite choice of materials. In this work we theoretically consider the metal-insulator-semiconductor heterojunction as a candidate for plasmonic hot-carrier photodetection and solar cells. The presence of the insulating layer can significantly reduce the dark current, resulting in increased device performance with predicted solar power conversion efficiencies up to 9%. For photodetection, the sensitivity can be extended well into the infrared by a judicious choice of the insulating layer, with up to 300-fold expected enhancement in detectivity.

Complementary probes for the electrochemical interface.

The functions of electrochemical energy conversion and storage devices rely on the dynamic junction between a solid and a fluid: the electrochemical interface (EI). Many experimental techniques have been developed to probe the EI, but they provide only a partial picture. Building a full mechanistic understanding requires combining multiple probes, either successively or simultaneously. However, such combinations lead to important technical and theoretical challenges. In this Review, we focus on complementary optoelectronic probes and modelling to address the EI across different timescales and spatial scales - including mapping surface reconstruction, reactants and reaction modulators during operation. We discuss how combining these probes can facilitate a predictive design of the EI when closely integrated with theory.

Single-site iron-anchored amyloid hydrogels as catalytic platforms for alcohol detoxification.

Constructing effective antidotes to reduce global health impacts induced by alcohol prevalence is a challenging topic. Despite the positive effects observed with intravenous applications of natural enzyme complexes, their insufficient activities and complicated usage often result in the accumulation of toxic acetaldehyde, which raises important clinical concerns, highlighting the pressing need for stable oral strategies. Here we present an effective solution for alcohol detoxification by employing a biomimetic-nanozyme amyloid hydrogel as an orally administered catalytic platform. We exploit amyloid fibrils derived from ß-lactoglobulin, a readily accessible milk protein that is rich in coordinable nitrogen atoms, as a nanocarrier to stabilize atomically dispersed iron (ferrous-dominated). By emulating the coordination structure of the horseradish peroxidase enzyme, the single-site iron nanozyme demonstrates the capability to selectively catalyse alcohol oxidation into acetic acid, as opposed to the more toxic acetaldehyde. Administering the gelatinous nanozyme to mice suffering from alcohol intoxication significantly reduced their blood-alcohol levels (decreased by 55.8% 300 min post-alcohol intake) without causing additional acetaldehyde build-up. Our hydrogel further demonstrates a protective effect on the liver, while simultaneously mitigating intestinal damage and dysbiosis associated with chronic alcohol consumption, introducing a promising strategy in effective alcohol detoxification.